This invention relates to carbon-containing refractories and in particular magnesite-carbon refractory brick suitable for use in metal processing equipment, especially basic oxygen furnaces (BOF), slaglines in ladles, electric arc furnaces, and ladle metallurgical furnaces. In these applications, the essential requirements for prolonged service are high hot strength and high slag resistance.
The traditional use of carbon-containing brick had been in the basic oxygen furnace. The brick most commonly used in the U.S. during the early 1960's was a pitch bonded or a burned pitch impregnated magnesite brick which contained about 5% max. residual carbon. In Europe, the practice of using pitch bonded or pitch impregnated burned dolomite brick evolved as the preferred BOF lining. In Japan, burned pitch impregnated brick containing about 70% MgO/30% CaO were favored.
In the late '70's and early ,80's a major breakthrough occurred in refractory technology for the BOF. The introduction of magnesite brick containing graphite had a major impact on prolonging service life of the brick to a new record number of heats. A series of magnesite-carbon brick were introduced which had a range of graphite from 3 to 30%. Depending upon shop practice certain more narrow ranges of graphite, for example, 10-12 or 15-17%, seemed to provide optimum service in certain furnaces. The major reason these types of brick gave increased service life was the increase in slag resistance offered by graphite.
In the late '70's, additions of fine metals like silicon, aluminum, magnesium and various alloy combinations of these metals were added to magnesite-carbon brick. These additions in minor levels ranging from 0 to 5 wt. % imparted increased hot strength and oxidation resistance to the refractory. The effect of the metals on hot strength depended on the type of metal used. For instance, aluminum and magnesium tended to increase hot strength, whereas additions of silicon had the opposite effect. Numerous patents, such as U. S. Pat. No. 4,306,030, describe this art. These additions noticeably extended lining life. It is believed the metals are capable of providing various functions. They can act as oxygen "getters" thereby consuming oxygen which otherwise would at higher temperatures be able to consume carbon, and if not involved with oxygen can at higher temperatures react with fine carbon derived from the brick's resin bond, pitch bond, or from pitch impregnation to produce carbides. The effect of the newly formed oxide or carbide phases is to lower the permeability of the brick, thereby allowing less oxygen or slag to enter into the brick which causes destructive reactions to occur. Another effect, especially with formation of aluminum carbides, was to significantly increase hot strength. Hot strength is perceived to be a very important parameter governing life of a refractory in demanding applications like the BOF. Refractories in such applications are under considerable mechanical and thermal stress. Simple fracture or spalling can often occur when the stresses become greater than the strength of the refractory lining.
Although major advances in lining life have been made with metal-containing magnesite-carbon brick, the addition of fine metals does have certain disadvantages. These disadvantages are the increased cost of the refractory due to the high cost of the metals, the safety considerations which must be dealt with in brick manufacture due to the explosive nature of the fine metals, the higher thermal expansion of brick made with metals which necessitates greater need for expansion allowances, and the increased hydration potential of metal-containing brick. There is also the concern that if the metal content becomes too high, slag resistance of the refractory may suffer because of the formation of low melting eutectics which has a deleterious effect on hot strength.
Because of these concerns with metal additions, research work was started in the development of metal-free or very low metal containing refractories. This work led to U.S. Pat. Nos. 4,912,068 and 4,957,887. It was found in the '068 patent that an improved metal-free magnesite-carbon refractory could be made if the purity of the magnesite and graphite were highly controlled. Brick of increased hot strength compared to metal-containing brick could be made by using deadburned magnesite of at least 98% MgO, less than 0.03% boron oxide, less than 0.3% silica, and having a lime/silica weight ratio above 2. The flake graphite purity had to be at least 98% carbon. A further advance in hot strength was made in the '887 patent where it was found that additional improvements within the high purity magnesite-carbon system could be made by adding to the base mix controlled levels of the fine metals. The levels were within the restricted range of 0.1 to 1 wt. % with any combination of the metals not exceeding 1 wt. %.
Table I outlines the evolution of the above-described magnesite-carbon brick and the changes in hot strength which have occurred with each advance. For purposes of discussion, hot strength is defined as the strength of the refractory when crushed at 2800.degree. F.
TABLE I __________________________________________________________________________ Comparison of Typical Hot Strengths of Magnesite-Carbon __________________________________________________________________________ Refractories Brick Type: Burned Magnesite Resin Bonded Metal-Containing Resin Bonded Resin Bonded Pitch Impregnated Mag-Carbon* Resin Bonded High Purity High Purity Mag-Carbon* Mag-Carbon** Mag-Carbon** Graphite Content, %: 0 17 17 17 17 Aluminum Content, %: 0 0 3 0 1.0 Crushing Strength at 2800.degree. F., 2830 2140 4700+ 2950 4410 psi: __________________________________________________________________________ *The magnesite used in these mixes had an MgO content of 96% and the flak graphite had an LOI of 96.5%. **The magnesite used in these mixes had an MgO content of 99% and the flake graphite had an LOI of 99%.
The major disadvantage of these compositions are the limited supply of expensive high purity magnesite and flake graphite. The need, therefore, exists to find a means of developing high hot strength in lower purity magnesite-carbon brick without the detrimental effects of adding large amounts of metals.